Virtual card service system and method

ABSTRACT

The present invention is fluorine-containing ethylene copolymer composition and a process of preparing same. The ethylene copolymers of the present invention are melt processible fluorinated copolymers having surface energies of less than about 25 dynes/cm.

This application claims the benefit of U.S. Provisional Application No.60/421,946, filed Oct. 29, 2002.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to fluorine-containing ethylene copolymercompositions having grafted fluorine-containing functionality. Thepresent invention also relates to polymer blends obtained fromfluorine-containing ethylene copolymers described herein. The presentinvention also relates to a process for preparing thefluorine-containing ethylene copolymers of the present invention.

2. Discussion of the Related Art

Fluoropolymer compositions are widely used for surface modification, asagents to impart desirable surface properties to various types ofsurfaces. For example, fluoropolymer compositions can impart or enhancethe water and oil repellency of certain surfaces, including fabrics andupholstery. However, surface treatment using fluoropolymers can involvecomplex processing steps to ensure that the fluoropolymer is applied andbonded to the surface being treated. The process can be difficult andexpensive. Organic solvent vapors can be released to the atmosphereduring the processing. Surface treatment can involve high temperaturecuring of the fluoropolymer to the substrate surface.

To impart water and oil repellency, fluorochemicals or fluoropolymerscan be dissolved or dispersed either in organic solvents or in water.For example, mixtures of fluorinated copolymers, mainly comprisingperfluoroalkyl methacrylate, and vinyl copolymers are disclosed in U.S.Pat. No. 3,277,039. U.S. Pat. No. 2,803,615 disclosesacrylate/methacrylate esters of N-alkyl or N-alkanolperfluoroalkanesulfonamides used to impart grease and oil repellency.Fluorochemical compositions for treating textile fibers and fabricscomprising an aqueous solution or dispersion of a fluorochemicalacrylate and a polyalkoxylated polyurethane having pendantperfluoroalkyl groups is described in U.S. Pat. No. 5,350,557. U.S. Pat.No. 5,536,304 describes a composition for imparting water and oilrepellency comprising a fluoroaliphatic radical containing agent, and acyclic carboxylic acid anhydride-containing polysiloxane.

Fluorochemicals can be melt-blended with thermoplastic polymers, andthereby impart water and oil repellency to the polymer by migrating tothe polymer surface as described in, for example, U.S. Pat. No.5,025,052, wherein the preparation of fluoroaliphatic radical-containingoxazolidinone compositions for blending with thermoplastic polymers isdescribed. U.S. Pat. No. 5,380,778 describes thermoplastic compositionscomprising fluoroaliphatic radical containing aminoalcohols and athermoplastic synthetic organic polymer.

Ethylene copolymers are useful polymeric materials in many applications.Ethylene copolymers can find use in applications such as packaging,laminate films, and adhesives for example. Conventional polyolefins suchas polypropylene, polyethylene, and conventional ethylene copolymershave high surface tension relative to fluoropolymers such aspolytetrafluoroethylene, for example. As a result, for applicationswherein water and oil repellency is important, articles made frompolyolefins must be treated to attain a satisfactory level ofrepellency. However, due to their relatively low melting point and lackof reactive functional groups, treatment of polyolefins withfluorochemicals or fluoropolymers is, in general, much more difficultthan treating other thermoplastic polymers.

Copolymers of ethylene and fluorine-containing monomers are known. Forexample, Tefzel®, manufactured by E.I DuPont de Nemours and Company, isa copolymer of ethylene and tetrafluoroethylene. Copolymers of this typeare very different from conventional polyethylene copolymers in manyaspects. For example, fluorine-containing ethylene copolymers aretypically melt-processable only at much higher temperature thanconventional ethylene polymers and ethylene copolymers, and theproperties of fluorine-containing ethylene copolymers differ formconventional ethylene copolymers. Copolymers of this type are notamenable to manufacture or processing under the type of conditions usedto manufacture and process conventional ethylene copolymers.Ethylene/fluoromonomer copolymers of this type are not compatible insystems that currently use polyethylene copolymers. For example, knownconventional ethylene/tetrafluoroethylene copolymers have no adhesion topolyethylene.

It would be desirable to have a fluorine-containing ethylene copolymerthat can be processed in the same way as conventional ethylenecopolymers. It would be desirable to have a melt-processablefluorine-containing ethylene copolymer. It would be desirable to have afluorine-containing ethylene copolymer that has a low surface tension.It would be desirable to have a fluorine-containing ethylene copolymerthat can be compatible with, or used in place of conventional ethylenecopolymers.

SUMMARY OF THE INVENTION

In one aspect, the present invention is a fluorine-containing ethylenecopolymer composition comprising: the product of the reaction between anethylene/glycidyl (meth)acrylate copolymer and a fluorine-containingcarboxylic acid.

In still another aspect, the present invention is a blend comprising atleast two thermoplastic materials wherein at least one is afluorine-containing ethylene copolymer composition comprising theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a fluorine-containing carboxylic acid.

In another aspect, the present invention is an article having a surfacewith a total surface energy of less than 25 dyne/cm comprising: afluorine-containing ethylene copolymer composition comprising theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a fluorine-containing carboxylic acid.

In another aspect, the present invention is a stain-resistant fibercomprising a fluorine-containing ethylene copolymer compositioncomprising the product of the reaction between an ethylene/glycidyl(meth)acrylate copolymer and a fluorine-containing carboxylic acid.

In still another aspect, the present invention is an article formed byinjection molding or by extrusion comprising a fluorine-containingethylene copolymer composition comprising the product of the reactionbetween an ethylene/glycidyl (meth)acrylate copolymer and afluorine-containing carboxylic acid.

In still another aspect the present invention is a mold release additivecomprising a fluorine-containing ethylene copolymer compositioncomprising the product of the reaction between an ethylene/glycidyl(meth)acrylate copolymer and a fluorine-containing carboxylic acid.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the present invention is a composition comprising afluorine-containing ethylene copolymer. The fluorine-containing ethylenecopolymer of the present invention can be obtained, for example, by theprocess of reactive melt compounding a glycidyl methacrylate containingethylene copolymer with a fluorine-containing material that alsoincludes carboxylic acid functionality. Reactive melt compounding, asthe term is used herein, includes any process whereby reactivecomponents are combined and reacted at temperatures above the meltingpoint of all of the reactive components. Reactive melt compounding doesnot require the presence of a solvent.

Suitable EGMA copolymers are copolymers obtained by copolymerization ofglycidyl methacrylate with ethylene. EGMA copolymers suitable for thepresent invention have a weight average molecular weight (M_(w)) of atleast 50,000. Preferably the M_(w) of EGMA copolymers suitable for useherein is in the range of from about 60,000 to about 200,000, morepreferably in the range of from about 70,000 to about 150,000, and mostpreferably in the range of from about 80,000 to about 120,000. Suitableethylene/glycidyl methacrylate copolymers (EGMA copolymers) can beobtained commercially from, for example, Aldrich Chemical Co.

EGMA copolymers suitable for use herein comprise from about 0.5 wt % GMAto about 30 wt %. Preferably EGMA copolymers comprise from about 2 wt %to about 18 wt % GMA, and more preferably from about 5 wt % to about 15wt %. Most preferably EGMA copolymers comprise from about 6 wt % toabout 12 wt % GMA.

Also EGMA copolymers suitable for use herein are terpolymers comprisingethylene, GMA and a third comonomer. Suitable third comonomers areselected from unsaturated carboxylic esters having from 3 to 12 carbons.Suitable third comonomers include, for example: n-butyl acrylate (nBA);methyl (meth)acrylate (M(M)A); ethyl (meth)acrylate; isobutyl acrylate(iBA); and vinyl acetate (VA). Methacrylate esters, for the purposes ofthe present invention, are suitable equivalents for acrylate esters forall purposes of the present invention. In the present invention ashorthand notation for “methacrylate and/or acrylate” can be either(meth)acrylate or, alternatively, (M)A. For example, in the presentapplication, a shorthand notation for “methyl methacrylate and/or methylacrylate” can be either “methyl (meth)acrylate” or, alternatively,“M(M)A”.

EGMA copolymers are reacted with fluorinated compounds having carboxylicacid functionality to yield the fluorine-containing ethylene copolymersof the present invention. Suitable fluorine containing carboxylic acidsare any such acids that can, after reaction with an EGMA copolymer orterpolymer, yield copolymers having surface energies of preferably lessthan about 25 dyne/cm. Perfluorocarboxylic acids and perfluoropolyethercarboxylic acids are preferred in the practice of the present invention.Suitable perfluorinated carboxylic acids can have from 2 to 30 carbonatoms, preferably from 4 to 24 carbons, more preferably from 6 to 20carbons, and most preferably from 6 to 18 carbons. Suitable acidsinclude, for example: perfluoro nonanoic acid (PFNON); perfluorooctanoic acid (PFOCT); perfluoro heptanoic acid (PFHEP); perfluorohexanoic acid (PFHEX). Perfluoropolyether carboxylic acids (PFPE)suitable for use in the practice of the present invention include PFPEof the general formula:CF₃—[CF(CF₃)—CF₂—O—]_(n)CF₂CO₂H;wherein n is an integer in the range of from about 5 to about 50.Preferably n is in the range of from about 12 to about 26, morepreferably in the range of from about 14 to about 24, and mostpreferably in the range of from about 16 to about 22. A suitable PFPE,for example, isα-(1carboxy-1,222-tetrafluoroethyl)-ω-[tetrafluoro(trifluoromethyl)ethoxy]poly[oxy[trifluoro(trifluormethyl)-1,2-ethanediyl]],which can be purchased commercially from E.I. DuPont de Nemours andCompany under the tradename of Krytox® 157FS.

EGMA copolymers can be reacted with suitable fluorine-containingcarboxylic acids by reacting the components in the melt, that is, at atemperature above the melting range of both reactants. Melt blending orcoextrusion of the components results in the acid-catalyzed ring openingof the three member heterocyclic ring (epoxide) of the GMA moiety toyield a perfluoroester of glycerol grafted to the ethylene copolymer(grafted fluoroester copolymer, or GFEC). A GFEC of the presentinvention can have a general formula as defined in any of Structures 1-3below.

wherein:ECOP is the ethylene copolymer backbone;R_(F) is a fluorine-containing acyl group suitable for use in thepractice of the present invention.A fluorine-containing ethylene copolymer product of the reaction asdescribed herein can be a complex mixture of any of the abovestructures, in addition to other reaction products obtained according tothe process described herein, in addition to unreacted startingmaterials. A composition of the present invention comprises GFEC havingany of Structures 1, 2 or 3 either individually present or present inany combination, in an amount of at least about 15 wt % of the totalcomposition. Preferably, the GFEC comprises at least about 20 wt % ofthe total composition. More preferably the GFEC comprises at least about25 wt %, and most preferably at least about 30 wt % of the composition.Of the GFEC present, preferably Structure 3 comprises less than 10 wt %of the combined total weight of the GFEC, more preferably less than 5 wt%, and most preferably less than 2 wt %.

In another embodiment, the present invention is a process for preparinga GFEC of the present invention. As noted hereinabove, a GFEC of thepresent invention can be obtained by reactive melt compounding asuitable glycidyl methacrylate-containing ethylene copolymer and asuitable fluorine-containing carboxylic acid. For a melt compoundingprocess according to the present invention, the components arepreferably combined at a temperature above about 160° C. but less thanabout 250° C. The components can be blended in the melt usingconventional mixing means, such as a Haake mixer, for example. Thecomponents can also be coextruded in the melt (reactive coextrusion) toobtain the GFEC product of the present invention.

EXAMPLES

The Examples and the Comparative Examples described herein are forillustrative purposes only, and not meant to limit the scope of thepresent invention in any manner.

Example 1

A mixture of 80.3 wt % EGMA copolymer (8 wt % GMA) and 19.7 wt % PFNONwas heated to a temperature of 180° C. and blended in a Haake mixer for10 minutes. The resulting material was then pressed between two Teflon®FEP plates at 180° C. for 10 minutes to form 10 mil thick films whichwere then cut into pieces. The film pieces were washed in an acetonebath for 2 days, and then rinsed for 1 minute in acetone and dried atroom temperature. The film samples were analyzed by infra red (IR)spectroscopy to show absorption in the region of 1787 cm⁻¹, indicativeof the carbonyl absorption of a perfluoroester group. The surface energywas analyzed and is reported in Table 1.

Examples 2-6

The process of Example 1 was repeated using the components in Table 1.

Comparative Examples 1-3

The procedure of Example 1 was repeated with the starting polymersindicated in Table 1, without added grafting agent. TABLE 1 SurfaceEnergy Measurements of 10 mil Compression Molded Film Total SurfaceStarting Energy Example Polymer Grafting Agent (dyne/cm) Comparative 1Teflon ® FEP None 19.1 Comparative 2 DPE 2020 None 33.8 Comparative 3E/8 wt % GMA None 27.6 Ex 1 E/8 wt % GMA 19.7 wt % PFNON 19.2 Ex 2 E/8wt % GMA 5.9 wt % PFPE 20.8 Ex 3 E/8 wt % GMA 11.1 wt % PFPE 16.6 Ex 4E/8 wt % GMA 17.9 wt % PFOCT 20.8 Ex 5 E/8 wt % GMA 16.1 wt % PFHEP 23.4Ex 6 E/8 wt % GMA 14.2 wt % PFHEX 20.5

1. A fluorine-containing ethylene copolymer composition comprising: theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a fluorine-containing carboxylic acid.
 2. Afluorine-containing ethylene copolymer composition comprising: theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a perfluorinated carboxylic acid, characterized in thatthe copolymer absorbs light in the region of from about 1750 cm⁻¹ toabout 1800 cm⁻¹ of the infra red absorption spectrum.
 3. A blendcomprising at least two thermoplastic materials wherein at least one isa fluorine-containing ethylene copolymer composition comprising theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a fluorine-containing carboxylic acid.
 4. A blendcomprising at least two thermoplastic materials wherein at least one isa fluorine-containing ethylene copolymer composition comprising theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a fluorine-containing carboxylic acid, characterized inthat the copolymer absorbs light in the region of from about 1750 cm⁻¹to about 1800 cm⁻¹ of the infra red absorption spectrum.
 5. An articlehaving a surface with a total surface energy of less than 25 dyne/cmcomprising: a fluorine-containing ethylene copolymer compositioncomprising the product of the reaction between an ethylene/glycidyl(meth)acrylate copolymer and a fluorine-containing carboxylic acid. 6.An article having a surface with a total surface energy of less than 25dyne/cm comprising: a fluorine-containing ethylene copolymer compositioncomprising the product of the reaction between an ethylene/glycidyl(meth)acrylate copolymer and a fluorine-containing carboxylic acid,characterized in that the copolymer absorbs light in the region of fromabout 1750 cm⁻¹ to about 1800 cm⁻¹ of the infra red absorption spectrum.7. A stain-resistant fiber comprising a fluorine-containing ethylenecopolymer composition comprising the product of the reaction between anethylene/glycidyl (meth)acrylate copolymer and a fluorine-containingcarboxylic acid.
 8. A stain-resistant fiber comprising afluorine-containing ethylene copolymer composition comprising theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a fluorine-containing carboxylic acid, characterized inthat the copolymer absorbs light in the region of from about 1750 cm⁻¹to about 1800 cm⁻¹ of the infra red absorption spectrum.
 9. An articleformed by injection molding or by extrusion comprising afluorine-containing ethylene copolymer composition comprising theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a fluorine-containing carboxylic acid.
 10. An articleformed by injection molding or by extrusion comprising afluorine-containing ethylene copolymer composition comprising theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a fluorine-containing carboxylic acid, characterized inthat the copolymer absorbs light in the region of from about 1750 cm⁻¹to about 1800 cm⁻¹ of the infra red absorption spectrum.
 11. A moldrelease additive comprising a fluorine-containing ethylene copolymercomposition comprising the product of the reaction between anethylene/glycidyl (meth)acrylate copolymer and a fluorine-containingcarboxylic acid.
 12. A mold release additive comprising afluorine-containing ethylene copolymer composition comprising theproduct of the reaction between an ethylene/glycidyl (meth)acrylatecopolymer and a fluorine-containing carboxylic acid, characterized inthat the copolymer absorbs light in the region of from about 1750 cm⁻¹to about 1800 cm⁻¹ of the infra red absorption spectrum.